Higher alkoxy-silicon halides



UNITED STATES PATENT OFFICE HIGHER ALKOXY-SILICON HALIDES Arthur .1. Barry, Midland, Mich, assignor to The Dow Chemical Company, Midland, Mich a corporation of Delaware No Drawing. Original application December 10,

1943, Serial No. 513,745. Divided and this application January 31, 1946, Serial No. 644,653

12 Claims. (Cl. 260462) This invention concerns certain new alkoxysilicon halides having the general formula:

water-repellent film of probably not more than 2 a few molecules, thickness, but such water-repellent film is usually short-lived and is readily removed, particuarly by washing with soapy water. In contrast the higher alkoxy-silicon hal- SlXi-(nh') 5 ides which are provided by the invention, when 11', applied to hydrophilic materials, form at the surface of the latter a. nearly invisible water- Wherem each R represents a hydrocarbOn repellent film which is far more durable and cal and at least one B represents an alkyl radiwhich is not readily removed by washing with cal containing 8 or more carbon atoms, 1ft rep- 10 water or soapy water Furthermore when after resents a monovalent hydrocarbon radical, X extensive use or prolonged washing, the Wate represents a halogen, e. g. fluorine, chlorine or repellent film starts to fail, the hydrophmc and and n are Whole numbers havmg base member becomes wetted in spots with water,- a sum not greater than 3, n being a number from the film may he rewriented at the surface f 1 to 3, inclusive, and n bemg a number from the base member merely by drying and washing 0 P 2, incluslvewhen in the general formula the material with an organic liquid such as ben- 15 greater than W the m may zene, toluene, chlorobenzene, carbon tetrachlosent the same or different radicals, and when n ride, ethylene chloride or propylene chloride, 15 greater than the symbols may repre' etc., so as again to render the surface of the sent the same or different radicals. The commaterial uniformly repellent to Watter j said general fonmulafl are usuafny In view of these facts it appears that the alkmoblle hqmds: although they may some oxy-silicon halides react with hydroxy groups stances q The compounds may "many at the surface of hydrophilic base members to be reacted 771th W hydroxyl split out hydrogen halide and form a chemical salts of carboxyhc acids, etc., which reactions inbond at an ester linkage, with the Surface 0f volve the splitting out of one or more halogen the base member It also appears that the atoms from the molecule 5' as a hydmhahc bility of the chemical bond, e. g. its resistance acid or a salt of such acid, with replacement of t0 cleavage by hydrolysis, varies depending on halogen by a radical of F compound the size of the alkoxy group or groups attached which the alkoxy-sillcon halide is reacted. For to the silicon atom and the bond t0 the base Instance; Such alkoxy'smcon halides m be member becomes more resistant to cleavage with PF W1th Wate1' to form correspondmg 'alkoxy increase in the number of carbon atoms in an silicols WhlCh often spontaneously undergo an alkoxy group connected With the Silicon atom mtermolfcular confiensatlon reactlon to form However, the invention is not restricted to this viscous liquid or solid products of high molecula theory as to the reason for the results obtained. Welght, they may be reacted Wlth hydroxy The observed fact is that alkoxy-silicon halides Compounds, alfiohols, phem )1 s cellulose, which contain an alkoxy radical having at least to form corresponding alkoxy silicon esters of eight carbon atoms form when applied to a Such hydroxy compounds Accordmgly, the hydrophilic substance, a water-repellent film alkoxy-silicon halides are useful as ma- 4o is far more pemlanenb formed .i gl lstfor thfi preiparation of variety of W 1 by treating the hydrophilic substance with an 8 V11 V98 alkloxy-silicon halide wherein the alkoxy groups The alkoxy-silicon halides containing an 1 each. contain a lesser number of carbon atoms, oxy radical having at least eight carbon atoms g or 1ess 1 are especially useful as agents for treating hy- The 'alkoxy-silicon halides of this invention are drop i ic su s having h o l ups at preferably prepared by reacting an aliphatic near the Surface renfier such Substances alcohol, having at least eight carbon atoms in repellent 2 water and for i Purpose the higher the molecule, with a polyhalo-silicon compound alkoxy silicon halides provided by the invention having the general formula. differ markedly from the lower alkoxy- (e. g. methoxyto hexoxy-) silicon halides previously R known to the art. Such lower, alkoxy-silicon wherein R represents a hydrocarbon or a hydrohalides may be applied to hydrophilic materials carbonoxy radical, X is a halogen, and n is a to form at the surface of the latter a temporary whole number of value ranging from 0 to 2, inclusive. Examples of such alcohol reactants are the silicon tricliloride, diedodecyl silicon dichloride,

phenyl silicon trichloride, diethoxy silicon dichloride, tolyloxy silicon trichloride and di-phen oxy silicon dichloride, etc.

The reaction between an alcohol and such polyhalo-silicon compound occurs readily and rapidly even at low'temperatures and care is taken to prevent the reaction from taking place violently. Usually the polyhalo-silicon compound is dissolved in an equal volume or more of an inert organic solvent, e. g. petroleum ether, ligroin, benzene, or ethylene chloride, etc., and the solution is cooled to below room temperature. The, alcohol reactant is then added in amount chemically equivalent to the halogen atoms to be displaced from the polyhalo-silicon compound used as a starting material. For instance, in the reaction of decyl alcohol with silicon tetrachloride, when monodecoxy silicon tri-, chloride is to be produced, the reactants are used in approximately equimolecular quantities, but when di-decoxy silicon dichloride is desired as the product, two molecular equivalents of the alcohol is used per mole of the silicon tetrachloride. If desired, a trihalo-silicon compound or a silicon tetrahalide may be reacted with two or more different alcohols, e. g. with octyl and dodecyl alcohols, to form a polyalkoxy-silicon halide such'as octyl dodecyl silicon dichloride. Such reactions of a polyhalo-silicon compound accomplished by contacting the hydrophilic mawith difierent alcohols are preferably carried 1 out in successive manner, since a good yield of a single polyalkoxy-silicon halide may be obtained when this is done, but the reactions of a' polyhalo-silicon compound with two or more different alcohols may be'carried out simultaneously if desired.

The reaction of an alcohol with a polyhalosilicon compound is exothermic and results in the evolution of a gaseous hydrogen halide.-

During the early stages of the reaction, the mixture is usually cooled, e. g. to maintain it at room temperature or below, but when the reaction has subsided or become less vigorous, the mixture may be heated under reflux to assure completion of the reaction. There are, of course, other ways in which the rate of the reaction may be controlled, e. g. the alcohol reactant may be added gradually to the polyhalo-silicon compound while maintaining the resultant mixture at above room temperature. When the reaction is complete (as evidenced by the fact that hydrogen halide is no longer evolved) the mixture is fractionally distilled to separate the alkoxysilicon halide product.

Any of a wide variety of materials which normally are hydrophilic may be rendered hydrophobic bytreatment with the alkoxy-silicon halide products. Examples of such hydrophilic materials are metals such as iron, aluminum, or magnesium; cellulosic materials such as cotton, rayon, or cellulose esters and-ethers in general; and various other materials such as glass, leather, wool, or rubber, etc. In treating cellustances, the alkoxy-silicon halides are best adapted for the treatment of woolen goods, or of hydrophilic inorganic substances, e. g. metals or glass, to render their surfaces repellent to water.

The alkoxy-silicon halides may be applied in concentrated form or as a solution in an organic diluent such asbenzene, toluene, or carbon tetrachloride, etc., to the hydrophilic base material by dipping, brushing, or spraying, or in other usual ways. In the instances in which the alkoxy-silicon halides are sufliciently volatile to form a vapor of the same, the treatment may. be

terial with such vapor. The treated material is thereafter washed with an organic solvent to re-.

move unadsorbed alkoxy-silicon halide from its I surface, or "preferably is washed with water or treated with steam tov hydrolyze such unadsorbed alkoxy-silicon halide and to remove the hy drohalic acid formed in the hydrolysis.

By such treatment the surfaces of iron, steel, orother metals may be rendered water repellent and, therefore, resistant to rusting or' other corrosive action such as is caused in part by moisture. Also, the surfaces of metals, glass, or ceramic ware, etc., may be provided with a. waterrepellent film which is adsorbtive to organic liquids and towhich paints, lacquers, varnishes, and the like adhere more firmly than to the hydrophilic base material itself. Accordingly, the foregoing treatment of inorganic hydrophilic base materials with the higher alkoxy-silicon halides provided by the invention is an excellent pretreatment preparatory to applying organic coatings, e. g. paint. or lacquer, to such base materials.

Thefollowing examples describe a number of ways in which the principle of the invention has been applied, but are not to be construed as limiting the "invention.

EXAMPLE 1 v In each of a series of experiments an alkoxysilicon halide was prepared by cooling a solution of a polyhalo-silicon compound, named in tive proportions of the same. It also names and describes the alkoxy-silicon halide products. In

those instances in which the foregoing general procedure was modified in any important re- Thereafter the mixture book of Standard Test Methods.

spect, the modification of the procedure is mentioned in the table.

occurred. The third piece of cloth which had been treated with tri-lauryloxy silicon chloride Table Rcoctants Product Polyhalo-Silicon Compound Alcohol Comments Kind Moles Kind Moles Name Properties 1. SiCli 1 ctanol-2 3 Tri-oct loxy silicon A mobile liquid of Product was not distilled. chlor de. lemon color. It probably includes minor amounts of di-octyloxy silicon dichloride and octyloxy silicon trichloride. 2. D ode cyl silicon l Iso-octyl alcohol. 2 Dodecyl di isooctyl- A liquid of pale yel- Product was not distilled.

trichloridc. oxy silicon chloride. low color. 3. SiCli l Louryl l Dodeooxy-silicon tri- Colorless liquid of Product was purified by dishlo de. B.P.l03ll0 C./ tillation.

mm. 4 do 1 ...do. 2 Di-dodecoxy silicon A colorless liquid Product was purified by disdichloride. distilling st 210- tillation. 5 do 1 do 3 'lri-dodecoxy silicon A liquid of light tan Product was not distilled.

. chloride. co or having aproximately the P. 9 C. G... Di-phenyl-silicon 1 do 1 Dodecoxy-di-phenyl Ali uid of pale tan Do.

dichloride. silicon chloride. co or. 7 Isoemylsilieon tri- 1 do 2 Di dodecory-isoemyl A liquid of lemon Do.

chloride. silicon chloride. co or. 8. SiCli l n-PropylOctadec- 1 Di-octadecoxy pro- Obtained as a pale Theoctadecylalcoholdidnot yl. 2 poxy silicon chloride. yellow solution in dissolve satisfactorily until hydrocarbon -solthe reaction mixture was vents. heated. Product was not isolatedbut wasnsedwhile in solution for the preparation of derivatives. 9 .do 1 n-Propyl Lauryl 1 Octadecoxy-do-dec- A liquid or ten color- ThaSiCh wesreactedwith a Octadecyl. l oxy-propoxy-silicon mixture of the alcohols.

. l hlorlde. product was not dis- In addition to the foregoing compounds I have also prepared tri-myricyloxy silicon chloride by the reaction of myricyl alcohol with silicon tetrachloride. In this instance, the product was obtained as a solution in the solvent used as the reaction medium and was not isolated. Instead, it was employed as a reagent for the preparation of other compounds while in said solution and was not isolated. Still other higher alkoxy-silicon halides may similarly be prepared. For instance, tridodecyloxy-silicon bromide may be prepared by reacting dodecyl alcohol with silicon tetrafbromide, or dioctyloxy silicon difluoride may be prepared by reacting octyl alcohol with silicon tetrafiuoride, etc.

EXAMPLE 2 Three pieces of cotton broadcloth having a count of 80x 160 threads per inch were immersed in a solution containing 3 per cent by weight of tri-lauryloxy silicon monochloride dissolved in a dry-cleaning liquid consisting essentially of a mixture of ethylene chloride and propylene chloride. The cloth was then air-dried until the drycleaning fluid had evaporated, after which it was washed with soapy water, rinsed and dried. It was then pressed with a flatiron heated to about 250 0., dry-cleaned, and again ironed. One piece of the cloth, thus treated, was tested for waterrepellency in accordance with the hydrostatic method described by Slowinskein Am. Dyestufl Reporter, 30, 7 (1941). It was found to withstand a hydrostatic pressure of 1'7 centimeters before penetration of water through the fabric occurred. A second piece of the cloth which had been treated with the tri-lauryloxy silicon chloride was subjected to 'the standard soap and water washing operation described on page 170 of the AATCC It was then dried and tested for water-repellency by the hydrostatic method. It also withstood a hydrostatic pressure'of 1'7 centimeters before leakage and ironed was subjected to dry-cleaning in a liquid mixture of ethylene chloride and propylene chloride, pressed with a hot iron until free of the cleaning fluid and then tested for water-repellency. It withstood a hydrostatic pressure of 15 centimeters before being penetrated by the water. The operations carried out with the cloth piece last mentioned show that the water-repellency was not reduced to any great extent by treatment with the dry-cleaning fluid (which is an excellent solvent for tri-lauryloxy silicon chloride) and indicates that the tri-lauryloxy-silicon radical has become chemically combined with the fabric. The pieces of cloth subjected to each of the foregoing treatments were well suited for use as water-repellent fabrics.

EXAMPLE 3 In two series of experiments, separate samples of a magnesium alloy, containing approximately 6 per cent by weight of aluminum, 3 per cent of zinc, 0.2 per cent of manganese and the remainder magnesium, were treated and thereafter tested for corrosion by salt water as follows: In one series of tests, samples of the alloy were "chrome- In the other series of experiments, samples of the same alloy which had been dichromate-coated" by the method described in treatment No. '7 on page 65 of the above-mentioned book, were employed. One sample of the dichromate-coated alloy was. tested directly for corrosion by salt water and another sample was dipped in the one per cent solution of di-octyloxy dodecyl silicon chloride, then heated at 150 C. for one hour and thereafter tested for corrosion. Each corrosion test was carried out by immersing a test piece in an aqueous sodium chloride solution of 3 per cent concentration, removing the test piece and permitting the liquor to drain therefrom and again immersing it in the brine. etc. These operations were carried out at room temperature and in regular cycles over a period of two weeks.

was examined to determine the extent to which it had been corroded. The following table identifies each test piece by stating whether. it was chrome-pickled" or was "dichromate-coated" and by stating whether it was treated with the dioctyloxy dodecyl silicon chloride. The table states -the portion of the metal surface which had suffered corrosion as per cent of the 7 total surface of the test piece.

Table Treated with Di-Octyloxy Dodecyl Silicon Chloride Per Cent Test new Corrosion No Yes N Yes Chrome-pickled.

V Dich romatc Coated.-

This application-isadivision of my copending Other modes of applying the principle of the application, Serial No. 513,745, flled December 10,

' invention may be employed instead of those exwherein each R-represents a hydrocarbon radical selected from the class consisting of alkyl radicals and aromatic hydrocarbon radicals'of the benzene series and at least one R is an alkyl radical containing at least '8 carbon atoms, R represents a monovalent hydrocarbon radical selected from the class consisting of alkyl radicals and aromatic hydrocarbon radicals of the benzene series, X represents a halogen, and n and n are whole numbers having afsmn not greater than 3, 11. being a number froml to 3 and n being a number from 0 to 2.

2. An organosilicon compound having the general formula:

wherein each R represents ahydrocarbon radical v selected from the class consisting of alkyl radicals and aromatic hydrocarbon radicals of the benzene series and at least one R is an alkyl rad- All of I the test pieces were initially of the same dimen-, sions. After completing the tests, each test piece "resents an alkyl radical, and n and n are whole ical containing at least 8 carbon atoms, R represents a monovalent hydrocarbon radical selected from the class consisting of alkyl radicals andv aromatic hydrocarbon radicals of the benzene series, and n and n are whole numbers having a sum not greater than 3.1: being a number from 1 to 3 and n being a number from 0 to 2.

3. An organosilicon compound having the general formula:

I Sick-gm) a wherein R represents an alkyl radical having at least 8 carbon atoms, R in eachoccurrence repnumbers having a sum not greater than 3, n being a number from 1 to 3 and n being a number from 0 to 2.

4. An organosilicon compound having the general formula: v

' (RD-l 81x44 wherein each R represents an alkyl radical containing at least 8 carbon atoms, x representsa halogen, and n is an integer not greater'than 3.

5. An organosilicon compound having the general formula:

wherein each R represents an alkyl radical containing 'at least 8 carbon atoms and n is an integernot greater than 3.

6. Anorganosilicon compound having the gen- 7 eral formula:

RO-BiCh wherein R is an alkyl radical containing at least 8 carbon atoms. I

7. An organosilicon compound having the general formula:

- (BO-l 28101:

wherein each R represents an alkyl radical containing at least 8 carbon atoms.

8. Di-dodecoxy silicon dichloride. 9. An organosilicon compound having th general formula:

(no-ham wherein each R represents an alkyl radical containing at least 8 carbon atoms and X represents ahalogen.

10. An organo-silicon compound having the general formula:

wherein each R represents an alkyl radical containing at least 8 carbon atoms.

11. Tri-dodecoxy silicon chloride. 1 12. An organosilicon compound having the general formula:

- wherein eachR represents a hydrocarbon radical selected from theclass consisting of alkyl radicals and aromatic hydrocarbon radicals of the benzene series and at least one R isan alkyl radical containing at least eight carbon atoms, R repre-- sents a monovalent hydrocarbon radical selected from the class consisting of alkyl radicals and aromatic hydrocarbon radicals of thebenzene 9 series, X represents a halogen, n and 11. each Number Name Date represent an integer from 1 to 2, and n and 1: 2,242,400 Loane May 20, 1941 have a sum not greater than 3. 2,394,642 Strain Feb. 12, 1946 H BARRY 5 OTHER REFERENCES REFERENCES CITED Uchlda: Chem. Absts, vol. 27 (1933), page. The following references are of record in the 3454- m f this patent; Volnov: Chem. Absts., VOL-34 (1940), pages T TES-P TENTS 5048-5049. m S A A 1o Kalinin: Chem. Absts., vol. 35 (1941), pag Number Name Date 2470.

2,053,474 Graves Sept. 8, 1936 

